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US3349097A - Water-soluble phthalocyanine dyestuffs and process for preparing them - Google Patents

Water-soluble phthalocyanine dyestuffs and process for preparing them Download PDF

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US3349097A
US3349097A US443084A US44308465A US3349097A US 3349097 A US3349097 A US 3349097A US 443084 A US443084 A US 443084A US 44308465 A US44308465 A US 44308465A US 3349097 A US3349097 A US 3349097A
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amino
benzene
methyl
parts
ethionylamino
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Kuhne Rudolf
Meininger Fritz
Noll Walter
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Hoechst AG
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Hoechst AG
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/523—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl amido or hydroxyalkyl amino sulfonyl group, a quaternised or non-quaternised amino alkyl sulfonyl amido group, or a substituted alkyl amino sulfonyl group, or a halogen alkyl sulfonyl amido or halogen alkyl amino sulfonyl group or a vinyl sulfonylamido or a substituted vinyl sulfonamido group
    • C09B62/525—Anthracene dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/4401—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system
    • C09B62/4403—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system the heterocyclic system being a triazine ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/523—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl amido or hydroxyalkyl amino sulfonyl group, a quaternised or non-quaternised amino alkyl sulfonyl amido group, or a substituted alkyl amino sulfonyl group, or a halogen alkyl sulfonyl amido or halogen alkyl amino sulfonyl group or a vinyl sulfonylamido or a substituted vinyl sulfonamido group
    • C09B62/537—Porphines; Azaporphines

Definitions

  • the arylamines of the aforesaid Formula 3 can be prepared by the reaction of carbylsulfate with nitroarylamines followed by the catalytic reduction of the nitroaryl compounds obtained containing N-ethionylamino groups as substituents.
  • the arylamines of the aforesaid Formula 4 can be prepared by the reaction of carbylsulfate with nitroarylamines followed by the catalytic reduction of the nitro aryl compounds obtained containing N-ethionylamino groups as substituents and saponifying the sulfuric acid ester grouping.
  • the condensation of the copper or nickel phthalocyanine-tetrasulfonic acid chloride with the amines of the composition indicated above is advantageously carried out in an aqueous medium in the presence of acid binding agents at a temperature between about 0 C. and 30 C. and a pH-value between about 4 and 9.
  • the reaction may be carried out in the presence of organic solvents such as acetone, methylene chloride or ethylene chloride.
  • N-ethionylaminoor N-isethionylamino-arylamines used in eX- cess or nitrogenous tertiary organic bases such as pyridine and picoline, or more advantageously inorganic compounds, such as sodium hydroxide solution, sodium bicarbonate, sodium carbonate, potassium carbonate, potassium bicarbonate or sodium acetate.
  • the condensation may also be carried out in an organic solvent free from water, such as pyridine, dimethylformamide, N-methylacetarnide or phosphoric acid-tris-dimethylamide, in the presence or absence of diluents, such as methylene chloride, acetone or methanol.
  • the condensation compounds containing N-isethionylamino groups can be converted into dyestuffs containing Nethionylamino groups by esterifying the hydroxyl groups of the isethionylamino groups with sulfuric acid or by reaction with acid salts, for example alkali metal salts of chlorosulfonic acid.
  • the condensation of the copperor nickel phthalocyanine-tetrasulfonic acid chlorides with arylamines of the composition indicated above may be carried out in such a manner that less amount of amine is used than it corresponds to the amount corresponding to the acid halide groups.
  • only one, two or three sulfonic acid chloride groups of the phthalocyanine-tetrasulfonic acid chloride can be reacted with the amines of Formula 1 or 2.
  • the remaining sulfonic acid chloride groups are then saponified to sulfonic acid groups so that, if desired, after esterification, dyestuffs are obtained which contain N- ethionylamino groups and also sulfonic acid groups.
  • the starting compounds copperor nickel phthalocyanine-tetrasulfonic acid chlorides are obtainable from copper or nickel phthalocyanine as described in US. Patent 2,219,330.
  • N-ethionylarnino arylamines there may be employed, for example, the following compounds (Table 1):
  • the products obtainable by the present invention are new. They are valuable water-soluble dystuffs. They are suitable for dyeing and printing various materials such as wool, silk, polyamides or polyurethanes by the usual dyeing methods, for example from a neutral to weakly acid bath in the presence of ammonium acetate.
  • the new dyestuffs are especially suitable for dyeing and printing materials containing cellulose, such as linen, regenerated cellulose and especially cotton.
  • the cellulose fibers are applied to the cellulose fibers by treating the material with an aqueous solution of the dyestuff at normal or raised temperature in the presence of an acid-binding agent, such as sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate or trisodium phosphate, or with a printing paste with the addition of an acid-binding agent, whereby the treatment with the acid-binding agent may be effected before, during or after the application of the dyestufi and by subsequently heating or steaming.
  • an acid-binding agent such as sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate or trisodium phosphate
  • the dyeings or prints so obtained are distinguished by good 'fastness properties, especially by a good fastness to light and very good fastness to wet properties. They possess furthermore a high brilliancy.
  • EXAMPLE 1 48.5 parts of copper-phthalocyanine-tetrasulfonic acid chloride (0.05 mol) (obtainable as described in U.S. Patent 2,219,330, Example 9) are pasted up with 100 parts by volume of water at C. and a suspension of 52.5 parts of the potassium salt of 4-(N-methyl-N-ethionylamino)-1-amino-benzene (0.15 mol) in 150 parts by volume of water and subsequently 5 parts of pyridine are added. By addition of dilute sodium hydroxide solution the pH-value is kept at 6.5. When the condensation is complete, the reaction mixture is diluted with 700 parts by volume of water and filtered at a temperature between 50 and 60 C.
  • the dyestulf is precipitated from the filtrate by sodium chloride, filtered off, washed and dried in vacuo at 60 C.
  • a water-soluble powder is obtained in a good yield. It dyes wool in fast turquoise blue tints. On cotton there are likewise obtained turquoise blue dyeings or prints of very good fastness properties.
  • EXAMPLE 3 48.5 parts of copper-phthalocyanine-tetrasulfonic acid chloride (0.05 mol) are pasted up with 100 parts by volume of water at 10 C. and a suspension of 17.4 parts of the potassium salt of 4-(N-methyl-N-ethionylamino)- 1-aminobenzene (0.05 mol) in 75 parts by volume of water and subsequently 5 parts of pyridine are added. By dropwise addition of a solution of sodium carbonate the pH- value is kept at 66.5. When the condensation is complete the reaction mixture is diluted with 500 parts by volume of water and clarified by suction at a temperature between 50 and 60 C.
  • the dyestuif is precipitated from the filtrate by potassium chloride, filtered-off, washed and dried in vacuo at 60 C.
  • a water-soluble powder is obtained in a good yield. It dyes cotton or wool in turquoise blue tints which possess good fastness properties.
  • the dyestufi is then precipitated by potassium chloride, filtered off by suction washed and dried in vacuo at 60 C. A water-soluble powder is obtained in a good yield. It dyes cellulose fibers in the presence of trisodium phosphate in turquoise blue tints which possess good fastness properties.
  • EXAMPLE 7 48.5 parts of copper-phthalocyanine-tetrasulfonic acid chloride (0.05 mol) are pasted up with 100 parts by volume of water at 10 C. and a suspension of 34.5 parts of 4-(N-rnethyl-N isethionylamino)-1-aminobenzene (0.15 mol) in parts by volume of water. and subsequently 5 parts of pyridine are added. The pH-value of the mixture is kept at 55.5 by dropwise addition of a solution of sodium carbonate. When the condensation is complete the reaction mixture is diluted with 500 parts of water and clarified at a temperature of about 50 C.
  • the dyestuff is then precipitated by addition of sodium chloride, filtered off by suction and dried in vacuo at 70-80 C. 30 parts of this condensation product are introduced ata temperature below 5 C. into 300 parts of concentrated sulfuric acid and stirred for one hour until it hasdissolved. This solution is then poured into a mixture of 2000 parts of a saturated potassium chloride solution and 1000 parts of ice. After stirring for half an hour, the precipitated dyestuff is filtered off by suction. The residue is repeatedly washed with a potassium chloride solution of 15% strength to remove most of the sulfuric acid. Then it is pasted up with 300 parts by volume of a potassium chloride solution of 15% strengthand neutralised by addition of sodium acetate to a pH-value of about 55.5.
  • EXAMPLE 9 48.5 parts of copper-phthalocyanine-tetrasulfonic acid chloride (0.05 mol) are pasted up with 100 parts by volume of water at 10 C. and a suspension of 11.5 parts of 4- (N-methyl-N-isethionylamino)-1-aminobenzene (0.05 mol) in 50 parts by volume of water and subsequently 5 parts of pyridine are added. The pH-value of the mixture is kept at 5 to 5.5 by dropwise addition of a solution of potassium bicarbonate. When the condensation is complete the reaction mixture is diluted with 500 parts by volume of water and clarified at a temperature of about 60 C. The resulting condensation product is then precipitated by the addition of sodium chloride, filtered oil and dried. 30 parts thereof are esterified in an analogous manner as described in Example 7. The resulting blue dyestufi" which is obtained in a good yield dyes wool in turquoise blue tints with good fastness properties.
  • EXAMPLE 10 48.5 parts of copper-phthalocyanine-tetrasulfonic acid chloride (0.05 mol) are pasted up with parts by volume of water at 10 C. and a suspension of 32.4 parts parts of 4-(N-isethionylarnino)-1-aminobenzene (0.15 mol) in 75 parts by volume of water and subsequently 5 parts of pyridine are added. The pH-value of the mixture is kept at 5 to 5.5 by dropwise addition of a solution of sodium carbonate. When the condensation is complete the reaction mixture is diluted with 500 parts by volume of water and clarified at a temperature of about 55 C. The condensation product is then precipitated by the addition of sodium chloride, filtered off and dried in vacuo at 7080 C.
  • EXAMPLE 13 48.25 parts of nickel-phthalocyanine-tetrasulfonic acid chloride (0.05 mol) obtainable in an analogous manner as described in US. Patent 2,219,330 are pasted up with 200 parts by volume of water at 10 C. and 52.5 parts of the potassium salt of 4-(N-methyl-N-ethionylamino)- l-aminobenzene (0.15 mol) are introduced and subsequently 5 parts of pyridine are added. By the addition of diluted sodium hydroxide solution the pH-value is kept at 6 to 6.5..When the condensation is complete the reaction miXture is diluted with 800 parts by volume of water and brought to 50 to 60 C.
  • the dyestulf is then precipitated by potassium chloride, filtered 01f, washed and dried in vacuo at about 60 C.
  • a water-soluble dark powder is obtained in good yield. It dyes wool in fast. greenish blue shades. .On cotton there are obtained in the presence of sodium bicarbonate greenish blue dyeings or prints of very good fastness properties and high brilliancy.
  • X represents a member.
  • n represents an integer from 1 to 3.

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Description

United States Patent This invention is a continuation-in-part application of US. patent application Ser. No. 155,497 filed Nov. 28, 1961, now abandoned, it relates to valuable new phthalocyanine dyestuffs and to a process for preparing them; in particular it relates to new phthalocyanine dyestuffs of the general Formula 1 Z mePc SOr-NH NSO2CH2CH2OSO3X I t wherein mePc represents copper or nickel phthalocyanine, X hydrogen or an alkali metal, R hydrogen or lower alkyl having from 1 to carbon atoms, Z hydrogen or halogen, such as chlorine or bromine, or lower alkyl or lower alkoxy, and n an integer from 1 to 3.
We have found that the valuable new phthalocyanine dyestuffs of the foregoing general Formula 1 are obtained by condensing 1 mol of a compound of the general Formula 2 mePc[SO Cl] wherein mePc is defined as above, with l to 3 mols of an N-ethionylaminoarylamine of the general Formula 3 IIzN or with 1 to 3 mols of an N-isethionylamino-arylamine of the general Formula 4 I\ITSO2CH2CH2OH i 4) in which Z, R and X are defined as above, and, if an amine of the general Formula 4 has been employed, converting the condensation product into the corresponding acid sulfuric acid ester. I
The arylamines of the aforesaid Formula 3 can be prepared by the reaction of carbylsulfate with nitroarylamines followed by the catalytic reduction of the nitroaryl compounds obtained containing N-ethionylamino groups as substituents. The arylamines of the aforesaid Formula 4 can be prepared by the reaction of carbylsulfate with nitroarylamines followed by the catalytic reduction of the nitro aryl compounds obtained containing N-ethionylamino groups as substituents and saponifying the sulfuric acid ester grouping.
The condensation of the copper or nickel phthalocyanine-tetrasulfonic acid chloride with the amines of the composition indicated above is advantageously carried out in an aqueous medium in the presence of acid binding agents at a temperature between about 0 C. and 30 C. and a pH-value between about 4 and 9. If desired, the reaction may be carried out in the presence of organic solvents such as acetone, methylene chloride or ethylene chloride.
As acid binding agents there may be used the N-ethionylaminoor N-isethionylamino-arylamines used in eX- cess or nitrogenous tertiary organic bases such as pyridine and picoline, or more advantageously inorganic compounds, such as sodium hydroxide solution, sodium bicarbonate, sodium carbonate, potassium carbonate, potassium bicarbonate or sodium acetate. The condensation may also be carried out in an organic solvent free from water, such as pyridine, dimethylformamide, N-methylacetarnide or phosphoric acid-tris-dimethylamide, in the presence or absence of diluents, such as methylene chloride, acetone or methanol.
The condensation compounds containing N-isethionylamino groups can be converted into dyestuffs containing Nethionylamino groups by esterifying the hydroxyl groups of the isethionylamino groups with sulfuric acid or by reaction with acid salts, for example alkali metal salts of chlorosulfonic acid.
The condensation of the copperor nickel phthalocyanine-tetrasulfonic acid chlorides with arylamines of the composition indicated above may be carried out in such a manner that less amount of amine is used than it corresponds to the amount corresponding to the acid halide groups. For example, only one, two or three sulfonic acid chloride groups of the phthalocyanine-tetrasulfonic acid chloride can be reacted with the amines of Formula 1 or 2. The remaining sulfonic acid chloride groups are then saponified to sulfonic acid groups so that, if desired, after esterification, dyestuffs are obtained which contain N- ethionylamino groups and also sulfonic acid groups.
The starting compounds copperor nickel phthalocyanine-tetrasulfonic acid chlorides are obtainable from copper or nickel phthalocyanine as described in US. Patent 2,219,330.
As N-ethionylarnino arylamines there may be employed, for example, the following compounds (Table 1):
Table 1 4-N-ethionylamino-l-amino-benzene 3-N-ethionylaminol-amino-benzene 2N-ethionylamino-l -amino-benzene 4-N-ethionylamino- 1 -amino-2-methyl-benzene 4-N-ethionylaminol -amino-2-methoxy-benzene 4-N-ethionylamino-1-amino-2-chloro-benzene 4-N-ethionylamino-l-amino-3 -methyl-benzene 4-N-ethionylamino-1-amino-3 -methoxy-benzene 4-N-ethionylamino-1-amino-3-chloro-bcnzene 4-N-ethionylamino-1-amino-2,S-dimethoxy-benzene 4-N-ethionylaminol -amino-2-methoxy-S-methyl-benzene 4-N-ethionylamino-1-amino-2-methoXy-benzene 4-N-ethionylamino-1-amino-3-ethoxy-benzene 3 -N-ethionylaminol-amino-4-methyl-benzene 3-N-ethionylamino-l -amino-4-methoxy-benzene 3 -N-ethionylamino-1-amino-4-ethoxy-benzene 3-N-ethionylaminol -amino-4-chloro-benzene 3 -N-ethionylamino-1-amino-4,6-dimethoxy-benzene Z-N-ethionylamino- 1 -amino-4-methyl-benzene Z-N-ethionylaminol -amino-4-methoxy-benzeue Z-N-ethionylamino-l-amino-4-chloro-benzene 2-N-ethionylamino-1-amino-5-methyl-benzene The novel dyestufis are obtained from a neutral or weakly acid solution by concentrating the solutions and/ or esparating the products by addition of a precipitating agent, such as sodium chloride or potassium chloride and by subsequently filtering and washing. The aqueous dyestuff pastes are dried at a temperature between 40 and 60 C., if desired, under reduced pressure in order to avoid decomposition of the dystuffs.
The products obtainable by the present invention are new. They are valuable water-soluble dystuffs. They are suitable for dyeing and printing various materials such as wool, silk, polyamides or polyurethanes by the usual dyeing methods, for example from a neutral to weakly acid bath in the presence of ammonium acetate. The new dyestuffs are especially suitable for dyeing and printing materials containing cellulose, such as linen, regenerated cellulose and especially cotton. They are applied to the cellulose fibers by treating the material with an aqueous solution of the dyestuff at normal or raised temperature in the presence of an acid-binding agent, such as sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate or trisodium phosphate, or with a printing paste with the addition of an acid-binding agent, whereby the treatment with the acid-binding agent may be effected before, during or after the application of the dyestufi and by subsequently heating or steaming.
The dyeings or prints so obtained are distinguished by good 'fastness properties, especially by a good fastness to light and very good fastness to wet properties. They possess furthermore a high brilliancy.
The following examples serve to illustrate the invention but they are not intended to limit it thereto. The parts being by weight unless otherwise stated and the relationship of parts by weight to parts by volume being the same as that of the kilogram to the liter.
EXAMPLE 1 48.5 parts of copper-phthalocyanine-tetrasulfonic acid chloride (0.05 mol) (obtainable as described in U.S. Patent 2,219,330, Example 9) are pasted up with 100 parts by volume of water at C. and a suspension of 52.5 parts of the potassium salt of 4-(N-methyl-N-ethionylamino)-1-amino-benzene (0.15 mol) in 150 parts by volume of water and subsequently 5 parts of pyridine are added. By addition of dilute sodium hydroxide solution the pH-value is kept at 6.5. When the condensation is complete, the reaction mixture is diluted with 700 parts by volume of water and filtered at a temperature between 50 and 60 C. The dyestulf is precipitated from the filtrate by sodium chloride, filtered off, washed and dried in vacuo at 60 C. A water-soluble powder is obtained in a good yield. It dyes wool in fast turquoise blue tints. On cotton there are likewise obtained turquoise blue dyeings or prints of very good fastness properties.
By using instead of the potassium salt of 4-(N-methyl- N-ethionylamino) 1 aminobenzene, the corresponding molar amounts of the following compounds in the form of their potassium salts there are obtained dyestuifs which possess similar properties.
Table 5 4-N-ethyl-N-ethionylaminol-amino-benzene 4-N-propyl-N-ethionylamino- 1 -amino-benzene 4-N-butyl-N-ethionylamino- 1 amino-benzene 4-N-pentyl-N-ethionylaminol -aminobenzene 4-N-methyl-N-ethionylamino-1-amino-2-methyl-benzene 4-N-methyl-N-ethionylaminol-amino-2-methoxybenzene 4-N-methyl-N-ethionylaminol-amino-2-ethoxy-benzene 4-N-methyl-N-ethionylaminol-amino-Z-chloro-benzene 4-N-ethyl-N-ethionylaminol -amino-2-methyl-benzene 4-N-butyl-N-ethionylamino-1-arnino-2-methoxy-benzene 6 4-N-methyl-N-ethionylamino-1-amino-3-methyl-benzene 4-N-methyl-N-ethionylamino-l-amino-3-methoxybenzene 4-N-methyl-N-ethionylamino-1-amino-3-chloro-benzene 4-N-methyl-N-ethionylamino-1-amino-2,5-dimethoxybenzene 4-N-methyl-N-ethionyla'mino-l-amino-2-methoxy-5- methyl-benzene 4-N-methyl-N-ethionylamino-1-amino-3-ethoxy-benzene 3-N-methyl-N-ethionylamino-l-amino-benzene 3-N-rnethyl-N-ethionylamino-1-amin0-4-methyl-benzene 3-N-methyl-N-ethionylamino-l-arnino-4-methoxybenzene 3-N-methyl-N-ethionylamino-1-amino-4-chloro-benzene 3-N-methyl-N-ethionylamino-1-amino-4-ethoxy-benzene 3-N-methyl-N-ethionylamino-l-amino-6-methyl-benzene 3-Nmethyl-N-ethionylamino-1-amino-6-methoxybenzene 3-N-methyl-N-ethionylamino-1-amino-6-chloro-benzene 3-N-methyl-N-ethionylamino-1-amino-6-ethoxy-benzene 3-N-methyl-N-ethionylamino-1-arnino-4,6-dimethoxybenzene 2-N-methyl-N-ethionylamino-l-amino-benzene Z-N-methyl-N-ethionylamino-l-amino-4-methyl-benzene Z-N-methyl-N-ethionylamino-1-amino-4-methoxybenzene Z-N-methyl-N-ethionylamino-1-amino-4-chloro-benzene 2-N-methyl-N-ethionylamino-l-arnino-S-methyl-benzene Z-N-methyl-N-ethionylamino-l-amino-S-methoxybenzene 2-N-methyl-N-ethionylamino-l-amino-S-chloro-benzene EXAMPLE 2 48.5 parts of copper phthalocyanine-tetrasulfonic acid chloride (0.05 mol) are pasted up with parts by volume of water at 10 C. and a suspension of 34.8 parts of the potassium salt of 4-(N-methyl-N-ethionylamino)-1- aminobenzene (0.1 mol) in 100 parts by volume of water and subsequently 5 parts of u-picoline are added. By the addition of sodium bicarbonate the pH-value is kept at 66.5. When the condensation is complete the reaction mixture is diluted with 700 parts by volume of water and clarified by suction at a temperature between 50 and 60 C. The dyestutf is precipitated from the filtrate by potassium chloride, filtered off, washed and dried in vacuo at 60 C. A water-soluble powder is obtained in a good yield. It dyes polyamides in fast turquoise tints. On cotton there are obtained turquoise blue prints or dyeings of very good fastness properties.
By using instead of the potassium salt of 4-(N-rnethyl- N-ethionylamino)-1-aminobenzene the corresponding molar amounts of the compounds listed in Table 5 in the form of their potassium salts there are obtained dyestuifs which possess similar properties.
EXAMPLE 3 48.5 parts of copper-phthalocyanine-tetrasulfonic acid chloride (0.05 mol) are pasted up with 100 parts by volume of water at 10 C. and a suspension of 17.4 parts of the potassium salt of 4-(N-methyl-N-ethionylamino)- 1-aminobenzene (0.05 mol) in 75 parts by volume of water and subsequently 5 parts of pyridine are added. By dropwise addition of a solution of sodium carbonate the pH- value is kept at 66.5. When the condensation is complete the reaction mixture is diluted with 500 parts by volume of water and clarified by suction at a temperature between 50 and 60 C. The dyestuif is precipitated from the filtrate by potassium chloride, filtered-off, washed and dried in vacuo at 60 C. A water-soluble powder is obtained in a good yield. It dyes cotton or wool in turquoise blue tints which possess good fastness properties.
Instead of the potassium salt of 4-(N-methyl-Nethionylamino)-1-aminobenzene there may be used the corresponding molar amounts of the compounds listed in Table 5 in the form of their potassium salts. The so obtained dyestuffs possess similar properties.
7 EXAMPLE4 48.5 parts of copper-phthalocyanine-tetrasulfonic acid chloride (0.05 mol) are pasted up with 100 parts by volume of water at 10 C. and a suspension of 50.1 parts of the potassium salt of 4-(N-ethionylamino)-1-aminobenzene (0.15 mol) in 150 parts by volume of water and subsequently parts of pyridine are added. By the addition of sodium acetate the pH-value is kept at 55.5. After completion of the condensation the reaction mixture is diluted with 500 parts by volume of water and clarified at a temperature of about 55 C. The dyestuff is then precipitated from the filtrate by potassium chloride, filtered off, washed and dried invacuo at 60 C. A water-. soluble powder is obtained in good yield. On cotton or regenerated cellulose there are obtained in the presence of sodium hydroxide or potassium hydroxide turquoise blue prints which possess good wet properties.
Instead of the potassium salt of 4-(N-ethionylamino)- l-aminobenzene there may be used the corresponding molar amounts of the following compounds (Table 6) in the form of their potassium salts. The resulting dyestuffs possess similar properties.
Table 6 3-N-ethionylaminol-aminobenzene 2-N-ethionylamino- 1 -aminobenzene 4-N-ethionylamino-1-amino-2-methyl-benzeue 4-N-ethionylamino-1-amino-2-chloro-benzene 4-N-ethionylamino-1-amino-3-methoxy-benzene 4-N-ethionylamino-1-amino-2-ethoxy-benzene 4-N-ethionylamino-1-a1r1ino-3-ethoxy-benzene 4-Nethionylamino-1-amino-3 -methyl-benzene 4-N-ethionylamino-1-amino-3-methoxy-benzene 4-N-ethionylamino-1-amino-3 -chloro-benzene 4-N-ethionylamino-1-amino-2,5-dimethoxy-benzene 4-N-ethionylamino- 1 -amino-2-methoxy-5 -met'hy1.-benzene 3 -N-ethionylamino-1-arnino-4-methyl-benzene 3-N-ethionylamino-1-amino-4-methoXy-benzene 3-N-ethionylamino-1-amino-4-ethoxy-benzene 3 -N-ethionylamino-1-amino-4-chloro-benzene 3-N-ethionylamino 1-amino-6-methyl-benzene 3-N-ethionylamino-1-amino-6-methoxy-benzene 3 -N-ethionylamino-1-amino-6-ethoxy-benzene 3-N-ethionylamino-1-amino-6-chloro-benzene 3-N-ethionylamino-1-amino-4,6-dimethoxy-benzene Z-N-ethionylamino-1-arnino-4-methyl-benzene 2-N-ethionylamino-1-amino-4-methoxy-benzene 2-N-ethionylamino-1-amino-4-chloro-benzene Z-N-ethiouylaminol-arnino-S-methyl-benzene Z-N-ethionylamino- 1 -arnino-5-methoxy-benzene Z-N-ethionylmaino-l-amino-S-chloro-benzene EXAMPLE 5 48.5 parts of copper-phthalocyanine-tetrasulfonic acid chloride (0.05 mol) are pasted up with 100 parts by volume of water at C. and a suspension of 33.4 parts of the potassium salt of 4-N-ethionylamino-l-amino-benzene (0.1 mol) in 100 parts by volume of water and subsequently 5 parts of pyridine are added. By addition of a solution of potassium hydrogen carbonate the pH-value is kept at 55.5. After completion of the condensation the reaction mixture is diluted with 500 parts by volume of water and clarified at a temperature of about 55 C. The dyestuif is then precipitated by potassium chloride, filtered olf by suction, Washed and dried in vacuo at 60 C. A water-soluble powder is obtained in a good yield. It dyes cotton in the presence of potassium hydroxide in turquoise blue tints which possess good fastness properties.
By using instead of the potassium salt of 4-N-ethionylamino-Laminobenzene the corresponding molar amounts of the compounds listed above in Table 6 in the form of their potassium salts there are obtained dyestuffs which possess similar properties.
3 EXAMPLE 6 48.5 parts of copper-phthalocyanine-tetrasulfonie acid chloride (0.05 mol) are pasted up With parts by volume of water at 10 C. and a suspension of 16.7 parts of the potassium salt of 4-N-ethionylamino-l-aminO- benzene (0.05 mol) in 70 parts by volume of water and subsequently 5 parts of pyridine are added. The pH-value of the mixture is kept at 5-5.5 by dropwise addition of a solution of sodium carbonate. When the condensation is complete the reaction mixture is diluted with 500 parts by volume of water and clarified at a temperature of about 55 C. The dyestufi is then precipitated by potassium chloride, filtered off by suction washed and dried in vacuo at 60 C. A water-soluble powder is obtained in a good yield. It dyes cellulose fibers in the presence of trisodium phosphate in turquoise blue tints which possess good fastness properties.
By using instead of the potassium sale of 4-(N-ethionylamino) l amino benzene the corresponding molar amounts of the compound listed above in Table 6 in the form of their potassium. salts there are obtained dyestuffs which possess similar properties.
EXAMPLE 7 48.5 parts of copper-phthalocyanine-tetrasulfonic acid chloride (0.05 mol) are pasted up with 100 parts by volume of water at 10 C. and a suspension of 34.5 parts of 4-(N-rnethyl-N isethionylamino)-1-aminobenzene (0.15 mol) in parts by volume of water. and subsequently 5 parts of pyridine are added. The pH-value of the mixture is kept at 55.5 by dropwise addition of a solution of sodium carbonate. When the condensation is complete the reaction mixture is diluted with 500 parts of water and clarified at a temperature of about 50 C. The dyestuff is then precipitated by addition of sodium chloride, filtered off by suction and dried in vacuo at 70-80 C. 30 parts of this condensation product are introduced ata temperature below 5 C. into 300 parts of concentrated sulfuric acid and stirred for one hour until it hasdissolved. This solution is then poured into a mixture of 2000 parts of a saturated potassium chloride solution and 1000 parts of ice. After stirring for half an hour, the precipitated dyestuff is filtered off by suction. The residue is repeatedly washed with a potassium chloride solution of 15% strength to remove most of the sulfuric acid. Then it is pasted up with 300 parts by volume of a potassium chloride solution of 15% strengthand neutralised by addition of sodium acetate to a pH-value of about 55.5. After filtering off the dyestufi is dried in vacuo at a temperature of about 5060 C. A water-soluble blue powder is obtained in a good yield. On cotton there are obtained in the presence of sodium carbonate dyeings or prints in turquoise blue tints which possess good fastness properties.
By using instead of the 4-(N-methyl-N-isethiony} amino)-l-aminobenzene the corresponding molar amounts of the following compounds (Table 7) and proceeding in an analogous manner there are obtained dyestuffs which possess similar properties.
Table 7 4-N-ethyl-N-isethionylaminol-amino-benzene 4-N-propyl-N-isethionylaminol-amino-benzene 4-N-butyl-N-isethionylaminol-amino-benzene 4-N-pentyl-N-isethionylamino-1-amino-benzene 4-N-methyl-N-isethionylamino-1-amino-2-methyl-benzene 4-N-methyl-N-isethionylaminol-amino-Z-methoxybenzene 4-N-methyl-N-isethionylamino- 1 -amino-2-ethoxy-benzene 4-N-methyl-N-isethionylamino-1 -amino-2-chloro-benzene 4-N-ethyl-N-isethionylamino-1-amino-2-methyl-benzene 4-N-butyl-isethionylamino-1-aminor2-methoxybenzene 4-N-methyl-Nisethionylamino-1-amino-3-methylbenzene 9 4-N-methyl-N isethionylamino-1-amino-3-methoxybenzene 4-N-methyl-N-isethionylamino-1-amino-3-chloro-benzene 4-N-methy1-N-isethionylamino-1-amino-2,5-dimethoxybenzene 4-N-methyl-N-isethionylamino-1-amino-2-methoxy-5- methyl-benzene 4-N-methyl-N-isethionylamino-1-amino-3-ethoxy-benzene 3-N-methyl-N-isethionylaminol-amino-benzene 3-N-methyl-N-isethionylamino-1-amino-4-butyl-benzene 3-N-methyl-N-isethionylamino-1-amin0-4-methoxybenzene 3-N-methyl-N-isethionylamino-1-amino-4-chloro-benzene 3-N-methyl-N-isethionylamino-1-amino-4-ethoxy-benzene 3-N-rnethyl-N-isethionylamino-1-amino-6-methyl-benzene 3-N-methyl-N-isethionylamino-1-amino-6-methoxybenzene 3-N-methyl-N-isethionylamino-1-amino-6-chloro-benzene 3-N-methyl-N-isethionylamino-1-arnino-6-ethoxy-benzene 3-N-methyl-N-isethionylamino-1-amino-4,6-dimethoxybenzene 2-N-methyl-N-isethionylaminol-amino-benzene Z-N-methyl-N-isethionylamino-1-amino-4-methyl-benzene 2-N-methyl-N-isethionylamino-1-amino-4-methoxybenzene 2-N-methyl-N-isethionylamino-1-amino-4-chloro-benzene Z-N-methyl-N-isethionylamino-l-amino-S-methyl-benzene 2-N-methyl-N-isethionylamino-l-amino-S-methoxybenzene 2-N-methyl-N-isethionylamino-1-amino-5-chloro-benzene EXAMPLE 8 48.5 parts of copper-phthalocyanine-tetrasulfonic acid chloride (0.05 mol) are pasted up with 100 parts by volume of water at 10 C. and a suspension of 23 parts of 4 (N methyl-N-isethionylamino)-1-aminobenzene (0.1 mol) in 100 parts by volume of water and subsequently 5 parts of pyridine are added. The pH-value of the mixture is kept at 55.5 by dropwise addition of a solution of sodium carbonate. When the condensation is complete the reaction mixture is diluted with 500 parts by volume of water and clarified at a temperature of about 50 C. The resulting condensation product is then precipiatated by the addition of sodium chloride, filtered olf and dried in vacuo at 7080 C. 30 parts of this condensation product are esterified in an analogous manner as described in Example 7. The resulting blue dyestul'f which is obtained in good yield gives on cotton or regenerated cellulose fibers in the presence of sodium bicarbonate turquoise blue tints or prints which possess good fastness properties.
Instead of 4 (N-rnethyl-N-isethionylamino)-1-aminobenzene there may be used the corresponding molar amounts of the compounds listed in Table 7 and proceeded in an analogous manner there are obtained dyestuffs which possess similar properties.
EXAMPLE 9 48.5 parts of copper-phthalocyanine-tetrasulfonic acid chloride (0.05 mol) are pasted up with 100 parts by volume of water at 10 C. and a suspension of 11.5 parts of 4- (N-methyl-N-isethionylamino)-1-aminobenzene (0.05 mol) in 50 parts by volume of water and subsequently 5 parts of pyridine are added. The pH-value of the mixture is kept at 5 to 5.5 by dropwise addition of a solution of potassium bicarbonate. When the condensation is complete the reaction mixture is diluted with 500 parts by volume of water and clarified at a temperature of about 60 C. The resulting condensation product is then precipitated by the addition of sodium chloride, filtered oil and dried. 30 parts thereof are esterified in an analogous manner as described in Example 7. The resulting blue dyestufi" which is obtained in a good yield dyes wool in turquoise blue tints with good fastness properties.
By using instead of 4-(N-methyl-N-isethionylamino)- l-aminobenzene the corresponding molar amounts of the compounds listed in Table 7 and proceeding in an analogous manner there are obtained dyestuifs which possess similar properties.
EXAMPLE 10 48.5 parts of copper-phthalocyanine-tetrasulfonic acid chloride (0.05 mol) are pasted up with parts by volume of water at 10 C. and a suspension of 32.4 parts parts of 4-(N-isethionylarnino)-1-aminobenzene (0.15 mol) in 75 parts by volume of water and subsequently 5 parts of pyridine are added. The pH-value of the mixture is kept at 5 to 5.5 by dropwise addition of a solution of sodium carbonate. When the condensation is complete the reaction mixture is diluted with 500 parts by volume of water and clarified at a temperature of about 55 C. The condensation product is then precipitated by the addition of sodium chloride, filtered off and dried in vacuo at 7080 C. 30 parts of this product are esterified in an analogous manner as described in Example 7. The resulting blue dyestufi" which is obtained in good yield in the form of a water-soluble powder gives on cotton in the presence of sodium hydroxide turquoise blue prints with good fastness properties.
By replacing 4-(N-isethionyl amino)-1-aminobenzene by the corresponding molar amounts of the compounds listed in the following Table 8 and proceeding in an analogous manner there are obtained dyestulfs which possess similar properties.
Table 8 4-N-isethionylaminol-amino-Z-methyl-benzene 4-N-isethionylarnino- 1 -amino-2-methoxy-benzene 4-N-isethionyl amino-1-amino-2-ethoxy-benzene 4-N-isethionylamino- 1 -amino-2-chloro-benzene 4-N-isetl1ionylamino-1-amino-3-methyl-benzene 4-N-isethionylamino-1-amino-3-methoxy-benzene 4-N-isethionylamino-1-amino-3-ethoxy-benzene 4-N-isethionylamino-1-amino-3-chloro-benzene 4-N-isethionylamino-11amino-2,S-dimethoxy-benzene 4-N-isethionylamino-1-amino-2-methoXy-5-methylbenzene 3-N-isethionylamino-1-amino-benzene 3-N-isethionylamino-l-amino-4-methyl-benzene 3-N-isetl1ionylamino- 1 -amino-4-methoxy-benzene 3-N-isethionylamino-1-amino-4-ethoxy-benzene 3-N-isethionylamino-1-arnino-4-chloro-benzene 3 -N-isethionylamino-1-amino-6-methyl-benzene 3 -N-isethionylamino-1-amino-6-methoxy-benzene 3-N-isethionylamino-1-amino-6-ethoxy-benzene 3 -N-isethionylamino-1-amino-6-chloro-benzene 3-N-isethionylamino-1-amino-4,6-dimethoxy-benzene 2-N-isethionylamino- 1 -amino benzene 2-N-isethionylamino-1-amino-4-methyl-benzene 2-N-isethionylamino-1-amino-4-methoXy-benzene Z-N-isethionylamino-1-amino-4-chloro-benzene 2-N-isethi'onylamino-1-amino-5-methyl-benzene Z-N-isethionylamino-1-amino-5-methoxy-benzene Z-N-isethionylarnino-l:amino-S-chloro-benzenc EXAMPLE 11 48.5 parts of copper-phthalocyanine-tetnasulfonic acid chloride (0.05 mol) are pasted up with 100 parts by volume of water at 10 C. and a suspension of 21.6 parts of 4-(N-isethionylamino)-1-aminobenzene (0.1 mol) in 75 parts by volume of water and subsequently 5 parts of pyridine are added. The pH-value of the mixture is kept at 5 to 5.5 by the addition of sodium bicarbonate. When condensation is complete the reaction mixture is diluted with 500 parts by volume of water and clarified at a temperature of about 60 C. The condensation product is then precipitated by the addition of sodium chloride, filtered ofi? and dried in vacuo at 70-80 C. 30 parts of this product are esterified in an analogous manner as described in Example 7. The resulting dyestutf which is obtained in good yield is a blue water-soluble powder which gives on cotton in the presence of trisodium phosmula lil
phate turquoise blue prints or dyeings which possess good fastness properties.
By replacing. the 4-(N-isethionylamino)-1-aminoben- EXAMPLE 12 48.5 parts of copper-phthalocyanine-tetrasulfonic acid chloride (0.05 mol) are pasted up with 100 parts by volume of water at 10 C. a suspension of 10.8 parts of 4-(N-isethionylarnino)-1-aniinobenzene (0.05 mol) in 50 parts by volume of water and subsequently 5 parts of picoline are added. The pH-value of the mixture is kept at 5 to 5.5 by the addition of sodium carbonate. When the condensation has finished the reaction mixture is heated to 50 C. and the condensation product is precipitated by the addition of potassium chloride, filtered off and dried in vacuo at.70-80 C. 30 parts of this condensation product are esterified in an analogousmanner as described in Example 7. The resulting dyestuff is obtained in good yield. It is blue Water-soluble powder which gives on cellulose fibers in the presence of potas: sium hydroxide turquoise blue prints or dyeings which possess good gastness properties.
By replacing the 4-(N-isethionylamino)-1-a rninobenzene by the corresponding molar amounts of the compounds listed in Table 8 by processing in an analogous manner there are obtained dyestuffs which possess similar properties.
EXAMPLE 13 48.25 parts of nickel-phthalocyanine-tetrasulfonic acid chloride (0.05 mol) obtainable in an analogous manner as described in US. Patent 2,219,330 are pasted up with 200 parts by volume of water at 10 C. and 52.5 parts of the potassium salt of 4-(N-methyl-N-ethionylamino)- l-aminobenzene (0.15 mol) are introduced and subsequently 5 parts of pyridine are added. By the addition of diluted sodium hydroxide solution the pH-value is kept at 6 to 6.5..When the condensation is complete the reaction miXture is diluted with 800 parts by volume of water and brought to 50 to 60 C. The dyestulf is then precipitated by potassium chloride, filtered 01f, washed and dried in vacuo at about 60 C. A water-soluble dark powder is obtained in good yield. It dyes wool in fast. greenish blue shades. .On cotton there are obtained in the presence of sodium bicarbonate greenish blue dyeings or prints of very good fastness properties and high brilliancy.
By replacing the potassium salt of 4-(N-methyl-N- ethionylamino)-1-aminobenzene by the corresponding molar amounts of the compounds listed above in Table 5 in the form of their potassium salts there are obtained dyestuffs which possess similar properties.
Starting with 48.25 parts of nickel-phthalocyanine- We claim:
1. A water-soluble.phthalocyanine dyestuflf of the formePc SO2-NH wherein InePc represents a member selected from the group consisting of copper phthalocyanine and nickel phthalocyanine, R represents a member selected from the group consisting of hydrogen and alkyl having from 1 to 5 carbon atoms, Z represents a member selected from the group consisting of hydrogen, chlorine, bromine,
lower alkyl and lower alkoxy, X represents a member.
selected from the group consisting of hydrogen and alkali metal, and n represents an integer from 1 to 3.
2. The dyestuff of the formula wherein Pc represents phthalocyanine and X is a member selected from the group consisting of hydrogen, sodium and potassium.
3. The dyestutf of the formula wherein Pc represents phthalocyanine and X represents a member selected from the group consisting of hydrogen, sodium and potassium.
4. The dyestuit of the formula wherein Pc represents phthalocyanine and X represents a member selected from the group consisting of hydrogen, sodium and potassium.
5. The dyestuff of the formula NiPc wherein Pc represents phthalocyanine and X, represents a memberselected from the group consisting of hydrogen, sodium and potassium.
6. A water-soluble phthalocyanine dyestuif of the formula Cu? 0 R N-SO CH CH O-SOX r r r wherein Pc represents phthalocyanine, R represents an alkyl group having from 1 to 5 carbon atoms, X repre-- sents hydrogen or alkali metal, and n represents the integer 1 or 2, the
(References on following page) 13 14 References Cited OTHER REFERENCES UNITED STATES PATENTS Farb. Hoechst A. G., Chemical Abstracts, vol. 61 (Oc 3,062,831 11/1962 Freyermuth et a1. 260-3145 wbEPZ619G4LPage1OSO8- FOREIGN PATENTS 5 WALTER A. MODANCE, Primary Examiner. 611,053 6/1962 Belgium- JAMES A. PATTEN, Examiner.
628,209 8/1963 Belgium.

Claims (1)

1. A WATER-SOLUBLE PHTHALOCYANINE DYESTUFF OF THE FORMULA
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US4033980A (en) * 1968-08-16 1977-07-05 Hoechst Aktiengesellschaft Phthalocyanine dyestuffs and process for preparing them

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DE1283997B (en) * 1965-01-02 1968-11-28 Hoechst Ag Process for the preparation of water-soluble phthalocyanine dyes
CH499582A (en) * 1968-10-03 1970-11-30 Ciba Geigy Ag Process for the preparation of acidic anthraquinone dyes
US4341699A (en) * 1979-07-13 1982-07-27 Sumitomo Chemical Company, Limited Reactive red dye having both monochlorotriazinyl- and vinylsulfone-type reactive groups
DE3033611A1 (en) * 1980-09-06 1982-04-29 Hoechst Ag, 6000 Frankfurt WATER-SOLUBLE DISAZO COMPOUNDS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS DYES
DE3584410D1 (en) * 1984-08-30 1991-11-21 Ciba Geigy Ag REACTIVE DYES, THEIR PRODUCTION AND USE.
DE3510180A1 (en) * 1985-03-21 1986-09-25 Hoechst Ag, 6230 Frankfurt WATER-SOLUBLE AZO COMPOUNDS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS DYES
DE3510179A1 (en) * 1985-03-21 1986-09-25 Hoechst Ag, 6230 Frankfurt WATER-SOLUBLE MONO AND DISAZO COMPOUNDS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS DYES
DE3517547A1 (en) * 1985-05-15 1986-11-20 Hoechst Ag, 6230 Frankfurt WATER-SOLUBLE DISAZO COMPOUNDS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS DYES
DE3517755A1 (en) * 1985-05-17 1987-01-15 Hoechst Ag WATER-SOLUBLE MONO AND DISAZO COMPOUNDS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS DYES
JPH089693B2 (en) * 1986-11-14 1996-01-31 住友化学工業株式会社 Triazine compound and method for dyeing or printing fiber material using the same

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